Grafting of a mixture of styrene and maleic anhydride onto backbone polymers containing active or labile hydrogen atoms

ABSTRACT

A process for preparation of carboxyl containing polymer products which comprises reacting polymers having active or labile hydrogen atoms with a mixture of styrene and maleic anhydride and carboxyl containing polymer products prepared thereby.

United States Patent 1 1 Gaylord A 13,41 GRAFTING or A MIXTURE orSTYRENE AND MALEIC ANHYDRIDE ONTO BACKBONE POLYMERS CONTAINING ACTIVE ORLABILE HYDROGEN ATOMS [75] Inventor: Norman G.

Providence, NJ.

[73] Assignee: Gaylord Associates, Newark, NJ.

[22] Filed: Feb. 24, 197-0 [21] Appl, No.: 13,768

Gaylord, New

[56] References Cited UNITED STATES PATENTS 1/1965 Cernia et al...260/878 R 4/1965 Jones et a1. ..260/878 R 2/1967 Moore ..260/886FOREIGN PATENTS OR APPLICATIONS 984,731 3/1965 Great Britain ..260/884850,471 10/1960 Great Britain... ....260/878 24,265 10/1964 Japan..260/878 OTI-IER PUBLICATIONS Polymer Letters, 8, pp 549-53 (1970)Kirk-Othmer, Encyclopedia of Chemical Technology, 12, p. 820, J. Wiley &Sons, New York (1967) Encyclopedia of Polymer Science and Technology, 1,p. 68, J. Wiley & Sons, New York (1964) Kirk-Othmer Encyclopedia ofChemical Technology,

19, pp. 56-7, J. Wiley 8!. Sons, New York (1969) l-Ieilbron (Ed.),Dictionary of Organic Compounds, III, p. 203, Oxford Univ. Press, NewYork (1953) I-Ieilbron (Ed.), Dictionary of Organic Compounds, IV p.2043, Oxford Univ. Press, New York (1965) Lange, Handbook of Chemistry(Sixth Ed.), p. 538-9 Primary Examiner-Harry Wong, Jr. AssistantExaminerA. Holler Attorney-E. J. Berry and L. Rosen [5 7] ABSTRACT Aprocess for preparation of carboxyl containing polymer products whichcomprises reacting polymers having active or labile hydrogen atoms witha mixture of styrene and maleic anhydride and carboxyl containingpolymer products prepared thereby.

15 Claims, No Drawings GRAFTING OF A MIXTURE OF STYRENE AND MALEICANHYDRIDE ONTO BACKBONE POLYMERS CONTAINING ACTIVE OR LABILE HYDROGENATOMS The invention relates generally to novel polymers containing freecarboxyl groups and a process for the Another object of the invention isto provide carbox- I yl-containing polymers which cannot be madesatisfac torily by known processes.

Another object of the present invention is to provide a new and novelprocess for the preparation of carboxyl-containing copolymers.

A further object is to react a mixture of styrene and maleic anhydridewith polymers having active hydrogen atoms and thereby obtain modifiedpolymer products having free carboxylic acid groups.

Other and further objects will become obvious from the detaileddescription of the invention presented hereinbelow.

It is known to be commercially desirable to have carboxyl functionalityincorporated into a polymeric structure. Various methods are known forachieving this functionality. Such carboxyl-containing polymers arecharacterized by their ability to participate in the formation ofcovalent, ionic and hydrogen bonds. As a result of this modification,the solubility properties, receptivity to dyes, adhesion to polar andnon-polar substrates including metals, permeability to gases includingwater vapor, interaction with fillers and reinforcing agents,compatibility and the ability to form polymer alloys of the polymers aregreatly improved.

The prior art teaches that certain carboxyl-containing polymers may beprepared by the copolymerization of an ethylenically unsaturatedcarboxylic acid with a suitable comonomer. This method is limited tomonomers which copolymerize with the unsaturated carboxylic acid andto'processes which are not made inoperable by the presence of anunsaturated carboxylic acid. Thus, an unsaturated carboxylic acid cannotbe incorporated using a polymerization system involving organometalliccatalysts, for example, as in the polymerization of ethylene to a highdensity polyethylene using an aluminum alkyl-titanium halide catalyst,in the polymerization of butadiene to essentially allcis-l,4-polybutadiene with an alkyl aluminum halide-cobalt octoatecatalyst, in the polymerization of propylene to polypropylene with analuminum alkyltitanium halide or alkylaluminum halide-titanium halidecatalyst and in the copolymerization of ethylene and propylene to anethylene-propylene copolymer with an alkylaluminum halide-vanadiumoxychloride catalyst.

An alternative method for preparing a carboxyl-containing polymer is thegrafting of an unsaturated acid on a polymer skeleton. For instance,acrylic or methacrylic acid can be grafted on polyethylene by the use ofhigh energy ionizing radiation (U.S. Pat. No.

3,211,808) while maleic anhydride is grafted on polyethylene by the useof benzoyl peroxide or azobisisobutyronitrile in the presence of air(Gabara and Porejko, J. Polymer Sci., A-l, 5, 1539 (1967). The need forspecial equipment is an obvious disadvantage of the radiation techniqueand, in addition thereto the formation of considerable amounts ofhomopolymer and/or the cross-linking of the base polymer aredisadvantages of both these processes.

Another method for incorporating carboxyl groups into a polymer is thereaction of unsaturated polymer with a carboxylic acid. Using thistechnique, a polyethylene wax with a molecular weight of from 1,000 toabout 5,000 and containing olefinic linkages is prepared by thepyrolysis or thermal degradation of high molecular weight polyethylene.The thus produced polyethylene wax is reacted with a carboxylic acidreagent such as maleic anhydride either in a melt or in solution (FrenchPat. No. 1,346,533). The disadvantage of this process is its relativelysevere limitation to unsaturated polymers.

Still another method for incorporating carboxyl groups in a polymerinvolves the ultraviolet irradiation of a solution containing anaromatic polymer such as polystyrene and maleic anhydride, as a resultof which irradiation, the aromatic ring forms an adduct with the maleicanhydride (US. Pat. No. 3,214,416). This process is also limited inscope since it requires special equipment and is only useful forpolymers containing aromatic rings.

Surprisingly, it has now been discovered that the addition of a mixtureof styrene and maleic anhydride to a polymer or copolymer which containslabile or active hydrogen atoms, in the absence of a radical catalyst,results in the formation of a carboxyl-containing polymer. This novelprocess is very broadly applicable to homopolymers and copolymers of allkinds.

In contrast to the known process of grafting of polymeric branches ontoa substrate polymer by generation of free radical sites on the latter asa result of hydrogen abstraction by a radical derived from a freeradical precursor or irradiation or shear, the carboxylation reaction ofthe present invention involves the insertion of a monomericstyrene-maleic anhydride charge transfer complex or a dimer or trimerthereof into a carbon-hydrogen bond of the substrate or trunk. polymeror copolymer.

The so-called trunk polymers which can be effectively carboxylated bythe process of the present invention constitute a broad group and may beany homopolymers or copolymers containing hydrogen atoms at leastlO-percent of which are active or labile hydrogen atoms, such hydrogenatoms falling into one or more of the following categories;

1. hydrogen atoms on tertiary or trisubstituted carbon atom,

2. hydrogen atoms on benzylic or allylic carbon atom,

3. hydrogen atoms on a carbon atom adjacent to an electron donor atom,

wherein X is nitrogen, sulfur or oxygen or other electron donor atom.

4. hydrogen atoms on a carbon atom adjacent to an electron acceptorgroup,

wherein X is carbonyl, carboxyl, carboxamide, carboxylate, thiocarbonyl,thiocarboxyl, thiocarboxamide, thiocarboxylate, nitrile, nitro, sulfonylor other electron acceptor group,

5. hydrogen atoms adjacent to a carbonyl group 6. hydrogen atomsadjacent to an electron donor atom wherein X is nitrogen, sulfur oroxygen or other electron donor atom.

The aforesaid required active hydrogen atoms may be present on theskeleton of the trunk polymer or on pendant groups attached to thepolymer.

Effective trunk or substrate polymers include but are not to be limitedto polymers derived from one or more of the following monomers:ethylene, propylene, butenes, higher a-olefms, styrene, vinyltoluene,butadiene, isoprene, chloroprene, allyl acetate, allyl chloride, vinylchloride, alkyl vinyl ether, vinyl acetate,

acrolein, alkyl acrylate, alkyl methacrylate, acrylonitrile,a-methacrylonitrile, acrylamide, methacrylamide, acrylic acid,methacrylic acid,

formaldehyde resins, silicones and poly[bis(chloromethyl)oxetane] aretypical useful substrate polymers.

Block and graft copolymers as well as alternating copolymers are aseffective as homopolymers and random copolymers provided they fullfilthe above criteria for having labile or active hydrogen atoms.

Naturally occurring polymers such as cellulose, starch, gelatin, silk,gum arabic and leather as well as derivatives of natural polymersincluding cellulose esters, carboxymethyl cellulose, hydroxyethylcellulose, oxidized cellulose, oxidized starch and cellulose nitrate arealso useful as trunk polymers.

The substrate polymer is reacted with a mixture of styrene and maleicanhydride. Although maleic anhydride is insoluble in styrene at roomtemperature, an equimolar mixture of the two forms a homogeneoussolution at 50-60 C. In order to prevent contamination of thecarboxyl-modified polymer with undesirable amounts of polystyrene orstyrene-maleic anhydride copolymer, as well as to prevent the graftingof long branches of a styrene-maleic anhydride copolymer on thesubstrate polymer, the monomer mixture used, should contain 11.5 molesof styrene per mole of maleic anhydride and preferably 1 mole of styreneper mole of maleic anhydride.

In carrying out the process of the invention, the solution of maleicanhydride in styrene is added, in the absence of a free radical catalystor solvent, to a molten or fluid polymer or copolymer which containslabile or active hydrogen atoms as hereinbefore characterized. Thestyrene solution of maleic anhydride is maintained at 50-60 C. in orderto prevent precipitation of the normally solid maleic anhydride. Thepolymer to which carboxylic groups are to be appended is heated to atemperature above 120 C. preferably 150-25 0 C., in order to convert itto a molten or fluid state. The temperature to which the polymer isheated is determined by the deformation or softening point of thepolymer, but in any case the temperature is preferably maintained above120 C.

The polymer is subjected to mechanical deformation in a suitable mixingdevice in order to continually expose new surfaces of the polymer to thesolution of maleic anhydride in styrene. Suitable mixing equipmentincludes a Banbury mixer, a Brabender Plasticorder, a rubber mill, ascrew extruder or any other of the well-known mechanical mixingequipment normally used in the mixing compounding, processing orfabrication of thermoplastic, elastomeric or thermosetting polymers.

The maleic anhydride solution in styrene is maintained above 50 C. butbelow C. and is added to the polymer which is being subjected todeformation at a temperature above C. The maleic anhydride solution isadded as rapidly as possible to the polymer substrate and the reactiontime may be varied from 1 minute to 1 hour. The carboxylation reactionactually occurs practically instantaneously when the carboxylicanhydride acid solution comes into contact with the heated polymeralthough the mixing time may be extended in accordance with the timeperiod and method necessary or available in order to discharge thereaction mixture from the mixing device.

The carboxyl content of the final carboxylated polymer product may bevaried from 0.1 to 50 percent by weight of the initial polymer orcopolymer by appropriate adjustment of reactant quantities.

The actual carboxyl content on a molar basis will depend upon themolecular weight of the original polymer and on the molecular weight ofthe monomer molecules in the polymer or copolymer. The carboxyl contentof the final carboxylated product may be varied from one carboxyl groupper two to 1,000 monomer units, the preferred range being one carboxylgroup per two to 100 monomer units.

The carboxyl groups in the polymer products are appended to thesubstrate polymer in conjunction with styrene units. Theycarboxyl-containing sites may be represented as follows:

EXAMPLE 1 Carboxylation of Poly (n-butyl acrylate) Thirty-five grams ofpoly (n-butyl acrylate) prepared by emulsion polymerization was reactedwith a mixture of 5.4 g. of styrene and 5.1 g. maleic anhydride,according to the process of the invention.

Into a Brabender Plasticorder chamber which was set at 75 RPM and atemperature of 150 C. there were added the 35 g. of poly (n-butylacrylate) which were allowed to flux.'A separately preparedstyrene-maleic anhydride solution was injected into the Brabenderchamber using a hypodermic syringe and the Brabender was allowed to runfor 10 minutes.

The reaction product was discharged and 41.7 g. of material recovered.The rubbery reaction product was cut into small pieces and extracted bymethanol for 24 hours using a Soxhlet extractor. The methanol-insolubleportion was dried to constant weight at 4050 C. under vacuum.

The methanol-insoluble portion was dissolved in acetone with stirringand slight heating. The solution was cooled to room temperature andtitrated with 0.1N methanolic KOH solution using a pH meter. The acidvalue was found to be 51 mg. KOH/g.

Since the carboxylated product should be converted to a half esterduring the extraction by methanol, according to the following equation:

the above-determined acid value corresponds to the carboxyl group of thehalf ester. Therefore, the actual acid value for the reaction productcontaining anhydride groups was calculated as 105 mg. KOH/g. Thecarboxyl number of the anhydride-containing product, calculated from theacid value, was 0.19 carboxyl groups per 100 g. of product.

EXAMPLE 2 Carboxylation of Polystyrene and cis-Polybutadiene Twohydrocarbon polymers, polystyrene and cispolybutadiene, were reactedwith the styrene-maleic anhydride carboxylation mixture in the BrabenderPlasticorder.

The conditions of the carboxylations and the characteristics of theresulting products are summarized in Table l. The acid value wasdetermined by suspending the carboxylated polymer in toluene, refluxingfor 1 hour with methanolic KOH and back-titrating the unreacted KOH with0.05N HCl in methanol. ln accordance with common practice (Garrett andGuile, J. Am. Chem. Soc., 73, 4533 (1951) for polymers containingstyrene-maleic anhydride units, the true acid value, reported in thetable, was obtained by multiplying by two the value obtained bytitration.

Prepared in toluene solution with benzoyl peroxide as polymerizationcatalyst; mol. wt. 40,500

** Prepared with diethylaluminum chloride-cobalt compound catalyst;polymer product with high (98%) cis-l ,4 structure used without removalof antioxidant.

EXAMPLE 3 Carboxylation of Miscellaneous Polymers using Styrene-MaleicAnhydride Carboxylation Mixture The general experimental procedure wasto set the Brabender Plasticorder at RPM and at the requiredtemperature. The polymer was added and allowed to flux. The addition ofmaleic anhydride-styrene solution, kept at 5060 C. was carried out andthe Brabender was run for an additional 10 minute period and discharged.The treated polymer was then pressed to give a film of about 2-3 mm.thickness. This sheet was cut into small strips and was then ground to20 mesh powder using a cutting mill. The powder was then extracted witheither acetone or methanol for 24 hours using a Soxhlet extractor. Theportion insoluble in acetone or methanol was dried, titrated withmethanolic sodium hydroxide and the acid value was then calculated. Theportion soluble in acetone or methanol was concentrated and poured intobenzene. The benzene insoluble part was found to be a styrene-maleicanhydride copolymer.

The details of the individual experiments and the results thereof areshown in Table II below. The acid value was determined as described inExample 2.

TABLEII other shapes. The films or sheets can be readily printed ordecorated, laminated to rigid or flexible substrates such as wood,paper, metals, thermoset polymers, other thermoplastic films, rubbersheeting, etc., used as adhesive films between plies in a multiplycomposite, e.g., wood-wood, wood-metal, metal-metal, as well asthermoplastic or thermoset polymer composites with wood, metal, glass,woven or non-woven fabrics or mats,

paper, etc., pressure or vacuum-formed, stretched,

Extraction by Acetone (A) or Methanol (M) Acid value of traction TimSoluble in insoluble in COOH min., Before, g. After, g. Insoluble A,insoluble A or M, groups] Polymer, g. Monomers, g. temp., sample samplein A or M, in benzene, mg. KOH/ 100 g. (See key below) 1:1 molar ratioweight weight percent percent g. sample product 10/120 24. 3(A) 24 J8. 8Trace 25 0. 04

10/100 24. 5(A) 22. 5 J2. 0 Trace 17 0. 03

10/170 25. 4(A) 24. 4 96. 2 Trace 25 0. 04

10/170 25. 2(M) 25. 2 100 Trace 86 0.

10/150 24. 7 (M) 23.0 93. 2 Trace 31 0. 06

10/150 25. 3(M) 22. 8 90. 2 Trace 56 0. 10 L g-g j 7. 0 10 150 25. 2(A)24. s 91. 5 Trace 76 0. 14

Calculated based on weight of sample before extraction.

STARTING POLYMERS AND IDENTIFICATION KEY A polypropylene density 0.906,melt index 15, un-

stabilized B polyethylene density 0.960, melt index 22 C polyethylenedensity 0.918, melt index 2 D ethylene propylene rubber (E 46%, P 54%) E4 medium molecular weight poly(vinyl chloride) containing 1% organo tinstabilizer F same as D G amorphous polypropylene I-I low molecularweight polyethylene molecular weight 2000 Iacrylonitrile-butadiene-styrene (ABS) resin J polyethylene density 0.96,melt index 0.7 K nitrile rubber with about 25% acrylonitrile content Lsame as D and F The carboxyl-containing polymers prepared by the processof the present invention may be fabricated into shaped objects byconventional fabrication methods. Due to the tendency ofcarboxyl-containing polymers to undergo intermolecular hydrogen-bonding,it may be necessary to increase processing temperature by 25"50C. toimprove the flow characteristics.

The carboxyl-containing polymers may be melt extruded into films,sheets, tubes, fibers, profiles and pressing. The incorporation ofblowing agents permits the production of foamed film or sheeting.

The fibers produced from the carboxyl-containing polymers by meltspinning or film splitting may be converted into woven and non-wovenstructures. Due to the presence of carboxyl groups the non-woven webs ormats have greater strength than the webs or mats produced from theunmodified polymers and in many cases, e.g., carboxyl-containingpolyolefins such as polyethylene or polypropylene, have paper-likecharacteristics. Both woven and non-woven structures may be coated orprinted with conventional paper or textile coating and printingcompositions to yield coated structures with good coating-substrateadhesion.

The carboxyl-containing fibers per se or in the form of woven ornon-woven structures are readily dyed with basic dyes, metal-containingdyes and reactive" dyes. The dyes may be incorporated in the polymermelt before spinning or extrusion.

The dyed or natural fiber mats or woven shapes may be laminated tosubstrates such as metals, wood, natural or synthetic fiber or filmstructures, etc. and yield composites with good interfacial adhesion.

The presence of carboxyl groups in the carboxylcontaining polymersincreases the adhesion and compatibility with inorganic or organicfillers such as silicates (clay, talc, mica, asbestos, wollastonite),oxides (aluminum oxide, hydrated alumina, magnesium oxide,

titanium dioxide, zinc oxide, quartz, diatomaceous earth), carbonates(calcium, barium and magnesium carbonates), hydroxides, carbon black,graphite, metal powders as well as glass in the form of powder, fibersor flake, lignin, keratin, wood flour, cotton flock and nylon, acrylic,alpha cellulose and rayon fibers. The fillers are generally blended withthe carboxyl-containing polymers prior to extrusion into films orfibers.

Filled or unfilled carboxyl-containing polymers may be extrusionlaminated onto suitable substrates such as wood, paper, metals, as wellas structures prepared from thermoplastic or thermosetting resins.

The carboxyl-containing polymers per se or blended with dyes, pigmentsor fillers may be compressed or injection molded into shaped objects.

The carboxyl-containing polymers may be crosslinked by treatment withsuitable polyvalent metal compounds, e.g., zinc acetate, basic aluminumacetate, zirconium acetyl acetonate. The cross-linking reaction iscarried out by treating the film, fiber or shaped object prepared fromthe carboxyl-containing polymer with an aqueous or organic solution ofthe metal compound. The carboxyl-containing polymer may also becompounded with metal oxides such as zinc oxide, magnesium oxide or leadoxide and extruded or molded into crosslinked shaped objects.

Treatment of the carboxyl-containing polymers with monovalent compoundssuch as sodium hydroxide, potassium hydroxide or lithium hydroxide maybe carried out by contacting the polymer with the solid inorganiccompound or with an aqueous solution thereof. The resulting salt form ofthe carboxyl-containing polymer has increased strength as well asmodified properties, e.g. increased water vapor permeability. The saltform can be extruded or molded into shaped objects.

Treatment of the carboxyl-containing polymer with a monovalent metalhydroxide, e.g. sodium hydroxide or ammonium hydroxide, or with anorganic amine such as triethylamine or ethanolamine increases the waterdispersibiiity. Aqueous dispersions prepared therefrom may be coated onsubstrates such as paper, wood or metal as well as fibers and, afterdrying, yield coated substrates with strongly adherent coatings.

The carboxyl-containing polymers may be converted into fine powders andused in the fluid bed coating of heated substrates, e.g. metal objects,to give adherent coatings. The powdered carboxyl-containing polymers mayalso be readily dispersed in aqueous amine or inorganic base solutions.7

The carboxyl-containing polymers are polyanionic in nature and may becombined with 'polycationic polymers to yield polyelectrolyte complexes.The latter are insoluble in water but are solubilized in simpleelectrolyte solutions, e.g. lithium chloride. In this form they may beconverted into membranes which are useful in dialysis and selectivefiltration.

In a most useful version of the present invention, the carboxylation ofa polymer with the styrene-maleic anhydride mixture may be carried outin an extruder and converted directly into a shaped object such as aninjaction molded shape or an extruded film and fiber. In this manner afiber or film containing carboxyl group may be prepared directly from anuntreated polymer by conducting the carboxylation reaction in theextruder barrel.

EXAMPLE 4 Carboxylated Polyethylene Film A conventional single screwextruder is heated to maintain a melt temperature of 230-260 C. for lowdensity polyethylene or 260-320 C. for high density polyethylene. Theextruder is modified so as to permit injection of the styrene-maleicanhydride carboxylation mixture into either the rear, center or frontheating zones. The pelletized polymer is fed into the cold end of thescrew extruder where it is heated and then transported by the revolvingscrew through the various heating zones. The styrene-maleic anhydridesolution previously heated to 60 C., is injected under nitrogen or otherinert gas pressure into the heated barrel through the appropriateopening into one of the heating zones where it comes in contact with thefluid polyethylene. The resultant molten carboxylated polyethylene istransported by the helical screw to a flat die for slot-die casting orto a circular die for blown-bubble extrusion.

The flat sheet which is extruded from the die is quenched by extrusiononto either a chilled drum or a liquid bath. The quenched film is theneither wound on a roll in the usual manner or stretched into an orientedfilm before winding on a roll.

The tube which is extruded from the circular die is expanded into abubble by internal air pressure, cooled by external air pressure andcollapsed by nip rolls before winding up on a roll.

The extruder may be equipped with a vent to remove any residual gaseousmonomer from the carboxylated polyethylene before extrusion through thedie.

EXAMPLE 5 Carboxylated polypropylene Fibers To process polypropylene avented extruder is heated so as to provide a melt temperature of 2703 20C. After carboxylation, as described in Example 4, the moltencarboxylated polypropylene is forced through a spinneret. The polymeremerging from the orifices in the spinneret is led to a cooling zonewhere it solidifies. The filaments of carboxylated polypropylene arethen stretched before winding on a spool or combined and twisted toproduce a multifilament yarn.

The monofilaments may be formed into a non-woven web after stretching.Alternatively the carboxylated polypropylene may be spun directly fromthe melt into a non-woven web and bonded in situ.

What is claimed is:

l. A process for production of a carboxyl-containing polymer whichcomprises adding a solution of maleic anhydride in styrene which ismaintained at a temperature of 50 to C. to a fluid polymer having activehydrogen atoms in the absence of a solvent at a temperature of aboveabout 120 C.

2. The process of claim 1 in which the mixture of styrene and maleicanhydride is maintained at a temperature of 50-70 C. and is added to thepolymer undergoing deformation.

3. The process of claim 1 in which the mixture of styrene and maleicanhydride contains 1 to 1.5 moles of styrene per mole of maleicanhydride.

4. The process of claim 1 in which the reaction is carried out at l50250C.

5. The process of claim 1 in which at least percent of the totalhydrogen atoms present on the polymer reacted are active hydrogen atoms.

6. The process of claim 5 in which the polymer reacted iscis-polybutadiene.

7. The process of claim 5 in which the polymer reacted is polystyrene.

8. The process of claim 5 in which the polymer reacted is polyethylene.

9. The process of claim 5 in which the polymer reacted is polypropylene.

10. The process of claim 5 in which the polymer reacted is polyvinylchloride.

11. The process of claim 5 in which the polymer reacted isethylene-propylene rubber.

12. The process of claim 5 in which the polymer reacted is a nitrilerubber.

13. The process of claim 1 in which the said reaction is carried outduring fabrication of said polymer to yield a carboxylated shapedpolymer productv 14. The process of claim 13 in which the product is afilm.

15. The process of claim 13 in which the product is a fiber.

2. The process of claim 1 in which the mixture of styrene and maleicanhydride is maintained at a temperature of 50*-70* C. and is added tothe polymer undergoing deformation.
 3. The process of claim 1 in whichthe mixture of styrene and maleic anhydride contains 1 to 1.5 moles ofstyrene per mole of maleic anhydride.
 4. The process of claim 1 in whichthe reaction is carried out at 150*-250* C.
 5. The process of claim 1 inwhich at least 10 percent of the total hydrogen atoms present on thepolymer reacted are active hydrogen atoms.
 6. The process of claim 5 inwhich the polymer reacted is cis-polybutadiene.
 7. The process of claim5 in which the polymer reacted is polystyrene.
 8. The process of claim 5in which the polymer reacted is polyethylene.
 9. The process of claim 5in which the polymer reacted is polypropylene.
 10. The process of claim5 in which the polymer reacted is polyvinyl chloride.
 11. The process ofclaim 5 in which the polymer reacted is ethylene-propylene rubber. 12.The process of claim 5 in which the polymer reacted is a nitrile rubber.13. The process of claim 1 in which the said reaction is carried outduring fabrication of said polymer to yield a carboxylated shapedpolymer product.
 14. The process of claim 13 in which the product is afilm.
 15. The process of claim 13 in which the product is a fiber.